The complex ［Mn(H2O)6］ (C13H10NO4S)2 {C13H10NO4S = 4-［(2-Hydroxy- benzylidene)-amino］- benzenesulfonic acid anion } was prepared in the CH3CH2OH/CH3OH solution, and the complex was characterized by elemental analysis, IR spectra, X-ray diffraction and TG-DTG analysis. The results show that the compound belongs to monoclinic system with space group P121/c1and cell parameters are as follows: a = 0. 633 48(2) nm, b = 3.564 08(8) nm, c = 0.944 25(3) nm, β = 131.790(2) °, V = 1.589 53(8) nm3 , Z = 2.Mn(II) is coordinated by six O atoms from six coordination waters, forming a deformed octahedral geometry. The deprotonated Schiff base is not participated in coordination, but as counter anion in the crystal structure, which makes the whole complex electrically neutral.